EP0101864A1 - Unsaturated copolymerisable polyesters, process for their preparation and their use - Google Patents

Abstract

The invention relates to unsaturated homo- and/or copolymerizable polyesters which have been prepared from an alcohol component comprising a multivalent alcohol, a carboxylic acid component comprising a multivalent carboxylic acid and optionally, hydroxycarboxylic acids or their derivatives capable of forming esters, and an acid component selected from the group consisting of maleic acid, fumaric acid, itaconic acid, mesaconic acid, aconitic acid, their derivatives capable of forming esters and mixtures thereof. As part of the alcohol coponent, hydroxylated polybutadiene with an average molecular weight of 2400 to 3000 and a hydroxy-functionality of 2.2 to 2.4 is condensed into the polyester. The polyesters exhibit useful flow anomalies which are due to their molecular structure.

Description

Unsaturated, homo- and / or copolymerizable polyesters, process for their preparation and their use

The invention relates to unsaturated, homo- and / or copolymerizable polyesters, prepared from at least partially polyhydric alcohols and at least partially polyhydric carboxylic acids and optionally hydroxycarboxylic acids or their derivatives capable of ester formation with the use of maleic acid, fumaric acid, itaconic acid, mesaconic acid and / or aconitic acid or their derivatives capable of esterification, a process for their preparation and their use.

The class of homo- and / or copolymerizable unsaturated polyesters, their preparation and their processing are known. For example, unsaturated polyester resins can be prepared by copolyesterification of mono- and / or polyhydric alcohols with mono- and / or polyhydric carboxylic acids and / or optionally hydroxycarboxylic acids with alcoholic hydroxyl groups or also by using or using their derivatives capable of ester formation. In this case, at least one compound comprising olefinically unsaturated, and homo- or copolymerizable _- bar, condensed into the polyester resin, wherein the Durchschnittsfunktiönalität and the ratio of hydroxyl to carboxyl groups after the professed rules must be selected from the prior art so that the formation of polyesters is guaranteed. These resins can then be cured in particular in thick layers to form thermosets, especially after the addition of radical-providing compounds and, if appropriate, after the addition of olefinically unsaturated copolymerizable monomeric compounds.

These known polyesters are used in particular in the form of their solutions in copolymerizable vinyl and / or allyl monomers as casting resins for impregnating electrical machines or parts thereof. With them e.g. Stators of electric motors or transformers impregnated using various impregnation processes such as dipping or trickling. Furthermore, electrical or electronic components or complete circuits can be coated on the surface with them.

After the machines or components have been immersed, they are passed through an evaporation and draining zone, and the adhering polyester resin is then cured in an oven. With this method, drip losses initially occur in the drip zone. If the resin obtained here can also be returned to the immersion container, there is the disadvantage that dripping leads to incomplete impregnation. Furthermore, additional drip losses occur in the oven before curing if the viscosity of the casting resins decreases due to the temperature increase. This is particularly disadvantageous because the material dripping in the oven hardens and not only can no longer be used, but also leads to considerable contamination of the oven.

Another problem that arises from the draining or draining of the casting resins used is the occurrence of uneven layer thicknesses increasing from top to bottom and the formation of beads on the lower edge of coated components.

To avoid these disadvantages, it is known to add structural viscosity or thixotropy to the casting resins by adding flow-producing anomalies. For this purpose, substances such as pyrogenic silica, asbestos fibers, quartz powder, microdolomite or else liquid components such as castor oil derivatives, acrylic resins or silicone resins are used. The use of these additives has several disadvantages. The inorganic components do not result in clear solutions, and their incorporation into the polyester resins is not always easy. The above-mentioned liquid components are disadvantageously present as plasticizers in the resins. Furthermore, when using the additives mentioned, skin formation of the casting resins can occur.

The object of the invention is to avoid these disadvantages of the prior art and to create polyesters which, owing to their molecular structure, have flow anomalies and exhibit pseudoplastic or thixotropic behavior without the addition of auxiliaries.

Surprisingly, it has now been found that this object can be achieved by incorporating long-chain alcohols into the polyesters, these long-chain alcohols replacing part of the customary low molecular weight alcohols.

The invention thus relates to unsaturated, homo- and / or copolymerizable polyesters of the type mentioned at the outset, which are characterized in that, as part of the alcohols, hydroxylated polybutatien with an average molecular weight of 2400-3000 and a hydroxy functionality of 2.2-2. 4 is condensed into the polyester.

The proportion of hydroxylated polybutadiene is advantageously 1-10 mol%, based on the total amount Alcohols. The polyesters modified in this way exhibit pseudoplastic or thixotropic behavior without the addition of the substances hitherto conventionally used to achieve the flow anomalies mentioned. When the content of _h ydroxyliertem polybutadiene of less than one percent of the effect of modification is too low, and at a content of more than 10% there is a risk of gelling.

From the large range of known knowledge about the production of unsaturated polyesters, a number of mono- and polyfunctional reactants can be mentioned below which can be used in the context of the invention. As alcohols e.g. to be used: alkanols such as methanol, ethanol, propanol, isopropanol, cyclohexanol, tetrahydrobenzyl alcohol, tricyclodecanol, benzyl alcohol and others, glycol propanediols, butanediols, hexanediols, trimethylhexanediol, cyclohexanedimethanol, 1,1-bis-hydroxymethylcyclohexane-3-ol, tricyclodecylodicyclodiol, tricyclodecylodicyclodiol, tricyclodicyclodiol, tricyclodecylodicyclodiol, tricyclodecylodicyclodiol, tricyclodecylodicyclodiol, tricyclodecylodicyclodiol,

The carboxylic acids can come into consideration lauric acid, oleic acid, benzoic acid, abietic acid and other monocarboxylic acids such as multivalent compounds succinic acid, adipic acid, ortho, iso and terephthalic acid, tetrahydrophthalic acid, hexachloroendo, tetrachlorophthalic acid, tetrabromophthalic acid, pyromellitic acid and other according to the state the technology for the production of unsaturated polyesters to be used.

Typical homo- or copolymerizable olefinically unsaturated compounds which are used for the production of unsaturated polyesters and are also used in the context of the invention are maleic acid, fumaric acid, itaconic acid, mesaconic acid and aconitic acid.

Also their functional derivatives such as esters, anhydrides, chlorides are used ter manner _- instead of the free alcohols or acids can in most.

It is essential to the invention that part of the alcohols usually used for the production ^/ of unsaturated polyesters is replaced by a hydroxylated polybutadiene with an average molecular weight of 2400 to 3000 and a hydroxy functionality of 2.2 to 2.4. A known, commercially available product of this type is liquid polybutadiene with terminal, primary hydroxyl groups, which are arranged 95% allylic. The microstructure of this polybutadiene was determined as follows: 60% 1,4-trans, 20% 1,4-cis and 20% vinyl configuration.

oder

modifiziert, in denen R¹ einen aliphatischen Rest, an dem die beiden zur Anhydridbildung befähigten Carboxylreste in 1,2- oder 1,3-Stellung stehen, R² einen Alkyl-oder Arylrest und X einen OH- oder C0₂H-Rest bedeuten, wobei gegebenenfalls die Verknüpfung der Hydroxylgruppen der stickstoffhaltigen Verbindungen an den Hydroxylgruppen des ungesättigten Polyesters mit Di- oder Triisocyanaten erfolgt sein kann.To increase the thermal durability of the unsaturated polyesters according to the invention in the hardened state, the polyesters are advantageous with nitrogen-containing compounds of the general formulas

or

modified in which R ^{1 is} an aliphatic radical on which the two carboxyl radicals capable of forming an anhydride are in the 1,2- or 1,3-position, R ^{2 is} an alkyl or aryl radical and X is an OH or C0 ₂ H radical , where appropriate the linking of the hydroxyl groups of the nitrogen-containing compounds to the hydroxyl groups of the unsaturated polyester can have been carried out with di- or triisocyanates.

As a simple representative of these nitrogen-containing compounds, which is particularly characterized by the imide ring I which is always present and can be used as an end group, the following compound (a) which can easily be prepared from phthalic anhydride and monoethanolamine is mentioned:

Modifications to this simple model can easily be achieved by choosing substituted, partially hydrogenated or more complicated derivatives of o-phthalic acid instead of simple phthalic anhydride, for example halogenated phthalic anhydrides (tetrachloro- or tetrabromophthalic anhydride), alkylated or hydrogenated systems (methyl Tetrahydro Hexahydro-, methylhexahydro-, endomethylene tetrahydrophthalic anhydride). A completely different design of ring I can be achieved by choosing compounds such as maleic or citraconic acid, succinic acid or derivatives and alkylated derivatives or the addition products of maleic or citraconic acid with dicyclopentadiene, unsaturated ketones or diolefins. However, compounds such as trimellitic anhydride may also be used. This acid, when reacted with a suitable amine, for example with monobutylamine, gives a building block in which the radical X is represented by the carboxyl radical on the aromatic ring.

Compounds such as 1,8-naphthalic acid or naphthalene-1,2-dicarboxylic acid in the form of their anhydrides also belong here (c, d), and further formula images (e to g) show further possible variations.

On the other hand, the simple ethanolamine can be replaced by a wide variety of amino compounds, for example by the isomeric propanolamines or butanolamines or other higher homologues, by phenyl ether alcohols or aminocarboxylic acids which are aminated in the core or by amine ethoxylation products of phenols which are aminated in the core.

This subheading also includes the reaction products of trimellitic anhydride formulated below, all of which correspond to the general formulation of a carboximide system outlined above, combined with a still active monofunctional group.

These or similar compounds, the production of which is not to be protected here, can be obtained in a manner known per se by heating or even only by moderate heating of the components in solution or melt and in many cases can be isolated as well-crystallized compounds. However, one can also proceed without isolating the products by either incorporating the product, which is prefabricated in the melt or in solution, like an ordinary monofunctional compound into the known structure of an unsaturated polyester by mixing in the other raw materials and heating them together, or by including melt-condensed the imide component with an already largely prefabricated unsaturated polyester that still contains free OH or COOH groups and immediately thereafter condensed with the prepared unsaturated polyester to the final product. In any case, the resistance limits and other properties of the imide building block must of course be taken into account.

End groups of di- or triisocyanates are added very smoothly, with either the prefabricated hydroxyl polyester being reacted with excess isocyanate

UP = ungesättigter Polyester
worauf an den noch aktiven NCO-Gruppen Umsetzung mit einem Hydroxyl-Imidbaustein erfolgen kann, oder man setzt zunächst ein Hydroxyl-Imidsystem mit überschüssigem Diisocyanat um und bringt dieses Produkt mit einem Hydroxylpolyester zur Reaktion:

UP = unsaturated polyester
whereupon the still active NCO groups can be reacted with a hydroxyl imide component, or first a hydroxyl imide system is reacted with excess diisocyanate and this product is reacted with a hydroxyl polyester:

As a monofunctional end group, these quite differently built imide units are decisive for the chain length, the molecular weight, the molecular shape and thus for the technically important viscosity.

In addition to these monofunctional imide units, imide residues can also be incorporated into the polyester via difunctional units. To this end, the polyester residues of a dicarboxylic acid, a dialcohol and / or a hydroxycarboxylic acid, each having at least one five-membered cyclic imide group, are advantageously condensed. The compounds containing one or more 5-membered cyclic imide groups to be used in polyester production must contain two functional groups which intervene in the formation reaction - of the unsaturated polyester resin. Divalent alcohols, dibasic carboxylic acids and / or hydroxycarboxylic acids or their derivatives capable of ester formation are considered here. They contain at least one 5-membered imide ring in their molecule. In a particularly important embodiment of the invention, the imide rings are arranged in the molecule in such a way that the functional groups which intervene in the polyester resin formation are connected to one another via different ring members of the imide rings. Corresponding dicarboxylic acids and dialcohols or hydroxycarboxylic acids are known per se, in particular from the prior art which deals with the production of saturated polyester resins containing imide rings. Reference should be made here, for example, to British Patent 9 73 377 or French Patent 13 68 741. They can be prepared by known processes, for example from compounds containing primary amino groups with compounds capable of forming cyclic imide groups and containing at least two carboxyl groups, with the proviso that that used to form a molecule containing imide groups Starting molecules together contain two groups capable of ester formation, which are not required for imide formation.

The compounds containing imide groups can be prepared separately and then added to the reaction mixture used to prepare the polyester, or they can also be formed directly in the reaction mixture from their starting materials in the presence of further components of the polyester resin, as is the case for saturated polyester resins, for example in the cited patents GB-PS 9 73 377 or FR-PS 13 68 741 is described. In this latter case, however, care must be taken that the unsaturated polyester components, in particular unsaturated polycarboxylic acids, are only added to the reaction mixture after sufficient, preferably complete, formation of imide rings in order to rule out undesirable side reactions. Groups capable of ester formation are primary or secondary alcoholic hydroxyl groups and carboxyl groups and groups derived therefrom, such as anhydrides, halides, esters, epoxides.

Examples of the compounds to be used according to the invention are substances of the following formulas which can be prepared from the starting materials listed in the 2nd and 3rd columns of the table below:

• 1)Tetracarbonsäuren und Aminoalkoholen,
• 2) Tetracarbonsäuren und Aminocarbonsäuren,
• 3) Tricarbonsäuren und Aminoalkoholen,
• 4) Tricarbonsäuren und Aminocarbonsäuren,
• 5) Tricarbonsäuren und prim. Diaminen,
• 6) Hydroxydicarbonsäuren und Aminoalkoholen,
• 7) Hydroxydicarbonsäuren und Aminocarbonsäuren,
• 8) Hydroxydicarbonsäuren und Diaminen,
• 9) Dicarbonsäuren und Aminodiolen,
• 10) Dicarbonsäuren und Aminodicarbonsäuren

From the listed compounds 1-16 it can be seen that, for example, reaction products

• 1) tetracarboxylic acids and amino alcohols,
• 2) tetracarboxylic acids and aminocarboxylic acids,
• 3) tricarboxylic acids and amino alcohols,
• 4) tricarboxylic acids and aminocarboxylic acids,
• 5) tricarboxylic acids and prim. Diamines,
• 6) hydroxydicarboxylic acids and amino alcohols,
• 7) hydroxydicarboxylic acids and aminocarboxylic acids,
• 8) hydroxydicarboxylic acids and diamines,
• 9) dicarboxylic acids and aminodiols,
• 10) Dicarboxylic acids and aminodicarboxylic acids

let use. Compounds which are composed of aromatic polycarboxylic acids and / or aromatic primary amines can be of particular importance. The resulting compounds, in which the imide rings are directly attached to or even participate in an aromatic ring, can be used for special purposes of the resins, e.g. in the field of electrical insulation.

The invention also relates to a process for the production of unsaturated homo- and / or copolymerizable polyesters from at least partially polyhydric alcohols and at least partially polyhydric carboxylic acids and optionally hydroxycarboxylic acids or their derivatives capable of ester formation with the use of maleic acid, fumaric acid, itaconic acid, mesaconic acid and / or Aconitic acid or its derivatives capable of ester formation, which is characterized in that hydroxylated polybutadiene having an average molecular weight of 2400 to 3000 and a hydroxy functionality of 2.5 to 2.4 is condensed into the polyester as part of the alcohols.

oder

mit eingesetzt oder der Polyester wird mit den stickstoffhaltigen Verbindungen der obigen allgemeinen Formeln umgesetzt, in denen R¹ einen aliphatischen Rest, an dem die beiden zur Anhydridbildung befähigten Carboxylreste in 1,2- oder 1,3- Stellung stehen, R² einen Alkyl- oder Arylrest und X einen OH- oder C0₂H-Rest bedeuten, wobei gegebenenfalls die Verknüpfung der Hydroxylgruppen der stickstoffhaltigen Verbindungen an den Hydroxylgruppen des ungesättigten Polyesters mit Di- .oder Triisocyanaten erfolgen kann.1-10 mol% of hydroxylated polybutadiene, based on the total amount of alcohols, is advantageously used. Nitrogen-containing compounds of the general formulas are advantageous in the production of the polyester

or

with or the polyester is reacted with the nitrogen-containing compounds of the above general formulas, in which R ^{1 is} an aliphatic radical on which the two carboxyl radicals capable of forming an anhydride are in the 1,2- or 1,3-position, R ^{2 is} an alkyl or aryl radical and X is an OH or C0 ₂ H radical, where the hydroxyl groups of the nitrogen-containing compounds can optionally be linked to the hydroxyl groups of the unsaturated polyester with di- or triisocyanates.

In another embodiment of the process according to the invention, residues of a dicarboxylic acid, a dialcohol and / or a hydroxycarboxylic acid each having at least one 5-membered cyclic imide group are advantageously condensed into the polyester.

The unsaturated polyesters are prepared in a known manner by melt condensation. Depending on the content of hydroxylated polybutadiene resin, more or less gelatinous unsaturated polyesters are formed in the melt at 200 ° C., which are readily soluble in styrene to unsaturated polyester resins. These show a very pronounced structural viscosity and thixotropy even at very high styrene contents.

The invention also relates to the use of a solution of the polyesters according to the invention in copolymerizable vinyl and / or allyl monomers, the proportion of polyester of which is 40-80% by weight and which additionally contains known hardeners and, if appropriate, accelerators and leveling agents, for impregnating electrical machines or Parts thereof and as a coating compound for electrical components and circuits. The polyester resins are therefore very suitable as impregnating resins in electrical engineering, for impregnating stators, rotors, transformers and other coils. The flow anomalies greatly reduce the drip loss both before curing and the drip loss during curing in the oven. This improves the filling of the cavities in the windings between the wires compared to conventional unsaturated polyester resin impregnants. This results in better strengthening of the windings and better heat dissipation from the windings.

By reducing the drip loss during curing in the oven, the economy is improved since less material than the drip loss in the oven has to be hardened and discarded. When the unsaturated polyester resins are used as a coating composition for electrical or electronic components and circuits, conventional fillers and / or reinforcing materials such as quartz powder, chalk, aluminum hydroxide or asbestos or glass fibers can be added to the resins. After adding suitable photoinitiators, these resins can also be cured by ultraviolet radiation.

The invention is explained in more detail below on the basis of exemplary embodiments.

example 1

1 mole of trimellitic anhydride, 5.8 moles of neopentyl glycol, 0.2 moles of terminally hydroxylated polybutadiene with an average molecular weight of 2800 and a hydroxy functionality of 2.2 to 2.4 6 moles of maleic anhydride and 3 moles of the reaction product from 1 mole of tetrahydrophthalic anhydride and 1 mole of monoethanolamine are mixed with 10 wt .-% xylene as an entrainer and melted and condensed in a flask with stirrer, thermometer, reflux condenser and nitrogen inlet tube. The maximum condensation temperature is 175 ° C. A mixture of xylene and water is distilled off. With an acid number of 40, the approach is rubbery. The temperature is now reduced to 140 ° C. and, after the addition of 0.001% benzoquinone, 30% styrene is slowly added to the batch. Despite the rubber-like consistency, the resin is readily soluble in styrene. After cooling to room temperature, the material shows a viscosity of approx. 6000 mPas (measured with a viscous scale, sphere 2). When standing, the resin gels into a gel-like one Mass that can be converted into a liquid state by stirring. The resin is diluted with styrene to a viscosity of 200 mPas and 1% tert-butyl perbenzoate is added as the hardener. 7 motorette coils consisting of 75 turns of a 1 mm thick copper wire are impregnated with the impregnating resin obtained in this way. After 15 minutes of draining at room temperature, the motorized coils impregnated in this way are cured in a forced air oven for 1 hour at 120 ° C. and for 1 hour at 140 ° C. The dripping loss observed in the oven is only between 3 and 5%.

Example 2

A linear polyester is prepared from 2.64 mol of diethylene glycol, 7.63 mol of tetrahydrophthalic anhydride, 7.6 mol of neopentyl glycol, 0.4 mol of hydroxylated polybutadiene according to Example 1 and 3.35 mol of maleic anhydride according to the procedure of Example 1. When the acid number is 44, the condensation is stopped and the product is dissolved in styrene. It is adjusted to a viscosity of 400 mPas at 23 ° C. with styrene. The polyester resin thus obtained is used to impregnate coils and to coat printed circuits by immersion. In turn, there are low dripping losses and an excellent impregnation or coating.

Comparative example

A polyester resin is prepared from 1 mol of trimellitic anhydride, 6 mol of neopentyl glycol, 6 mol of maleic anhydride and 3 mol of the reaction product from 1 mol of tetrahydrophthalic anhydride and 1 mol of monoethanolamine. The viscosity is adjusted with styrene as in Example 1. When using this polyester resin to impregnate motor coil

there is a drip loss of 11 to 15% in the oven.

Claims (10)

1. Unsaturated, homo- and / or copolymerizable polyester, prepared from at least partially polyhydric alcohols and at least partially polyhydric carboxylic acids and optionally hydroxycarboxylic acids or their derivatives capable of ester formation with the use of maleic acid, fumaric acid, itaconic acid, mesaconic acid and / or aconitic acid or their Derivatives capable of ester formation, characterized in that hydroxylated polybutadiene with an average molecular weight of 2400 to 3000 and a hydroxy functionality of 2.2 to 2.4 is condensed into the polyester as part of the alcohols. 2. Polyester according to claim 1, characterized in that the proportion of hydroxylated polybutadiene is 1 to 10 mol% based on the total amount of alcohols. 3. Polyester according to claim 1 or 2, characterized in that the polyester with nitrogen-containing compounds of the general formulas

or

are modified in which R ^{1 is} an aliphatic radical on which the two carboxyl radicals capable of anhydride formation are in the 1,2- or 1,3-position, R ^{2 is} an alkyl or aryl radical and X is an OH or C0 ₂ H radical mean, where the linkage of the hydroxyl groups of the nitrogen-containing compounds to the hydroxyl groups of the unsaturated polyester with di- or triisocyanates may have been carried out. 4. Polyester according to claim 1 or 2, characterized in that in the polyester residues of a dicarboxylic acid, a dialcohol and / or a hydroxycarboxylic acid are each condensed with at least one 5-membered cyclic imide group. 5. A process for the preparation of unsaturated, homo- and / or copolymerizable polyesters from at least partially polyhydric alcohols and at least partially polyhydric carboxylic acids and optionally hydroxycarboxylic acids or their derivatives capable of ester formation using maleic acid, fumaric acid, itaconic acid, mesaconic acid and / or aconitic acid or their derivatives capable of ester formation, characterized in that hydroxylated polybutadiene having an average molecular weight of 2400 to 3000 and a hydroxy functionality of 2.2 to 2.4 is condensed into the polyester as part of the alcohols. 6. The method according to claim 5, characterized in that 1 to 10 mol% of hydroxylated polybutadiene based on the total amount of alcohols are used. 7. The method according to claim 5 or 6, characterized in that be "1 of the preparation of the polyester nitrogenous compounds of the general formulas

or

are used with or the polyesters are reacted with the nitrogen-containing compounds of the above general formulas in which R ^{1 is} an aliphatic radical on which the two carboxyl radicals capable of forming an anhydride are in the 1,2- or 1,3-position, R ^{2 is} an alkyl or aryl radical and X is an OH or C0 ₂ H radical, it being possible for the hydroxyl groups of the nitrogen-containing compounds to be linked to the hydroxyl groups of the unsaturated polyester with di- or triisocyanates. 8. The method according to claim 5 or 6, characterized in that in the polyester residues of a dicarboxylic acid, a dialcohol and / or a hydroxycarboxylic acid are each condensed with at least one 5-membered cyclic imide group. 9. Use of a solution of the polyesters according to Claims 1 to 4 in copolymerizable vinyl and / or allyl monomers, the proportion of polyester of which is 40-80% by weight and which additionally contains known hardeners and optionally accelerators and leveling agents for Impregnation of electrical machines or parts thereof. 10. Use of a solution of the polyesters according to Claims 1 to 4, in copolymerizable vinyl and / or allyl monomers, the proportion of polyester of which is 40-80% by weight and which additionally contains known hardeners and optionally accelerators and leveling agents, as a coating composition for electrical and / or electronic components and circuits.